High compliance, high strength catheter balloons useful for treatment of gastrointestinal lesions

ABSTRACT

Balloon especially useful for dilatation of gastrointestinal lesions have a burst pressure of at least 9 atmospheres, a diameter at 3 atmospheres of about 5 mm or more, and an average compliance over the range of from 3 atmospheres to burst of at least 3% per atmosphere. Such balloons and balloons having other combinations of burst strength, compliance and diameter may be prepared by a method wherein a tubing of a thermoplastic polymer material is radially expanded under a first elevated pressure at an elevated temperature to form the balloon at a first diameter and then annealing the balloon at a second elevated temperature and a second pressure less than the first elevated pressure for a time sufficient to shrink the formed balloon to a second diameter less than the first diameter. The thermoplastic polymer material may be a block copolymer material. Catheters bearing balloons prepared by this method have low withdrawal force requirements, especially catheters used in through-the-scope applications.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. application Ser. No.11/009,355 filed Dec. 10, 2004, incorporated herein by reference in itsentirety, allowed, which is a continuation of U.S. application Ser. No.08/685,338, filed Jul. 23, 1996, which is a continuation-in-part ofcopending U.S. application Ser. No. 08/397,837, filed 2 Mar. 1995, nowU.S. Pat. No. 5,556,383, which is a continuation-in-part of Ser. No.08/204,554, filed Mar. 2, 1994, now abandoned.

BACKGROUND OF THE INVENTION

Balloons mounted on the distal ends of catheters are widely used inmedical treatment. The balloon may be used to widen a vessel into whichthe catheter is inserted or to force open a blocked vessel. Therequirements for strength and size of the balloons vary widely dependingon the balloon's intended use and the vessel size into which thecatheter is inserted.

Perhaps the most demanding applications for such balloons are in balloonangioplasty in which catheters are inserted for long distances intoextremely small vessels and used to open stenoses of blood vessels byballoon inflation. These applications require extremely thin walled,high strength, relatively inelastic balloons of predictable inflationproperties. Thin walls are necessary because the balloon's wall andwaist thicknesses limit the minimum diameter of the distal end of thecatheter and therefore determine the limits on vessel size treatable bythe method and the ease of passage of the catheter through the vascularsystem. High strength is necessary because when the balloon is used topush open a stenosis, the thin wall must not burst under the highinternal pressures necessary to accomplish this task. The balloon musthave some elasticity so that the inflated diameter can be controlled,enabling the surgeon to vary the balloon's diameter as required to treatindividual lesions, but that elasticity must be relatively low so thatthe diameter is easily controllable. Small variations in pressure mustnot cause wide variation in diameter. Such angioplasty balloons havenominal diameters in the range of from about 1.25-4.5 mm.

Outside the field of angioplasty, however, relatively high compliant,high strength materials are desirable for some balloons used onesophageal, pyloric, colonic and anastomotic catheters and scopes.

Major advances in the ability to access remote areas within thegastrointestinal tract have allowed endoscopists to reach obstructivelesions previously accessible only via open surgical techniques. Thereare three primary approaches available to the clinician for endoscopictreatment of gastrointestinal strictures: 1) Mercury bougie dilatation;2) Over-the-wire passage of tapered dilators; and 3) Balloon dilation.

Of the three, balloon dilatation is the most recently developedmodality. Clinical research studies have been conducted to compare theefficacy of the technique to earlier approaches. For example, in onestudy evaluating Savary-Guillard® Dilators versus balloon dilators fordilatation of benign esophageal strictures, both methods achievedeffective dilatation. However, during the 24 month follow-up, 88% ofpatients treated with Savary dilators required redilations vs 54% ofpatients in the balloon group. As a result, the researchers concludedthat, over the long term, the balloon may provide superior efficacy.Additional studies have clearly documented the convenience,effectiveness and safety of balloon dilatation of strictures.

An important advantage of balloon dilatation over the alternativetechniques is that it enables the clinician to dilate remote stricturesthroughout the GI tract.

An example is the treatment of esophagal achalasia. The esophagus, ahollow, muscular organ that originates at the pharynx and terminates atthe stomach, functions to transport food and fluids from the pharynx tothe stomach via a complex, neuromuscular response to the act ofswallowing. Specifically, the passage of food or fluid from the pharynxinto the esophagus stimulates the peristaltic contractions designed topropel the contents forward through the esophagus. Concurrently, thelower esophageal sphincter (LES) at the gastroesophagal junction relaxesallowing the passage of esophagal contents into the stomach. Reflux ofstomach contents back into the esophagus is prevented by closure of theLES. Achalasia is a disorder of unknown etiology that disrupts thenormal esophageal function (3,4). In this disorder, two deficits arepresent. First, the normal esophagal peristaltic wave is absent. Second,the lower esophageal sphincter does not relax. The result is esophagealdilatation and severe, progressive dysphagia. Treatment for achalasia isaimed at reduction of LES pressure. This is accomplished nonsurgicallyvia forceful balloon dilatation of the sphincter.

Biliary dilatation may also be performed by such balloon catheterdilatation. Biliary strictures may result from variety of processesincluding postoperative scarring, inflammation, or malignancy.Endoscopic balloon dilatation of these lesions has been shown to be aneffective treatment approach.

There therefore is a need for effective devices which permit endoscopicdilatation of lesions throughout the alimentary tract. It is importantthat the catheters offer first-use effectiveness in an advanced designto permit rapid inflation, deflation and easy scope passage. Theballoons for such devices desirably would have a long dilation length,high operating pressure, typically greater than 50 psi (3 atm, 344.7kPa) and desirably up to 146 psi, (10 atm, 1013 kPa), low withdrawalforce and high compliance. For instance, a compliance change isdesirable which would allow a balloon having a 1.25-3.0 mm nominaldiameter at 3 atm to grow in a generally linear manner at least 0.25 mm,preferably about 0.5 mm, or more as pressure is increased from 3 to 12atm. For balloons about 3.25-6.0 mm nominal diameter, a growth of atleast 1.0 mm over the same range would be desirable. For balloons in therange of about 6-12 mm nominal diameter, a growth of at least 2.0 mmover a 3-10 atm pressure range would be desirable. For even largerdiameter balloons, for instance balloons having 3 atm diameters of 12-30mm, a compliance curve which provides growth of about 3 mm or more,preferably about 4.0 mm or more, over the range of 3 to 9 atm isdesirable.

In U.S. Pat. No. 5,348,538, incorporated herein by reference, there isdescribed a single layer angioplasty balloon made of a material such asPET which follows a stepped compliance curve. The stepped compliancecurves of these balloons have a low pressure segment following a firstgenerally linear profile, a transition region, typically in the 8-14 atmrange, during which the balloon rapidly expands yielding inelastically,and a higher pressure region in which the balloon expands along agenerally linear, low compliance curve. The stepped compliance curveallows a physician to dilate different sized lesions without usingmultiple balloon catheters.

A polyethylene ionomer balloon with a stepped compliance curve isdisclosed in EP 540 858.

In copending U.S. application Ser. No. 08/397,837, filed 2 Mar. 1995,entitled Block Copolymer Elastomer Catheter Balloons, incorporatedherein by reference, which corresponds to WO 95/23619, there aredescribed balloons, useful on angioplasty catheters and similar medicaldevices, which are made from certain block copolymer materials whichprovide an unusual combination of compliance, softness and strengthproperties.

Block copolymer balloons for balloon catheters, prepared using aparticular heat set technique to stabilize the balloon dimensions, arealso described in U.S. Pat. No. 5,500,180.

SUMMARY OF THE INVENTION

The invention provides balloons having the desired properties justdescribed. In one aspect, the invention is a method for forming aballoon for a medical device in which a tubing of a thermoplasticpolymer material is radially expanded under a first elevated pressure ata first elevated temperature to form the balloon at a first diameter,the thermoplastic polymer material being a block copolymer material andthe method including the further step of annealing the balloon at asecond elevated temperature less than or equal to the first temperatureand a second pressure less than the first elevated pressure for a timesufficient to shrink the formed balloon to a second diameter less thanthe first diameter. Suitably the second temperature is in the range of70-100° C., the second pressure is no more than about 50 psi, and thetime of annealing is sufficient to shrink the balloon so that itsdiameter at 3 atm pressure is about 90% or less, preferably about 85% orless, of the 3 atm diameter of a correspondingly prepared balloonprepared without said shrinking step.

In some embodiments to improve balloon-to-balloon reproducibility of theprocess, the balloon may be shrunk at a very low inflation pressure(typically 0-10 psi) to a nominal diameter below that desired in thefinal balloon, and then pressurized at a pressure between the shrinkpressure and 50 psi, at a temperature within the same range within amold or cylinder which is sized to provide the desired nominal diameter,still below the diameter at which the balloon was initially blown, andsuitably 90% or less of the initial blow diameter.

The shrinking process used in the invention is quite different from theheat set technique used in U.S. Pat. No. 5,500,180, in that the processof U.S. Pat. No. 5,500,180, after formation of the balloon heats theballoon under pressure of 100-500 psi to a temperature above the blowingtemperature specifically for the purpose of stabilizing the balloonagainst shrinkage upon cooling. The present invention is directed toexploitation of shrinkage behavior in order to increase the complianceof the resulting balloon.

Balloons made of multiple layers of thermoplastic material, such ascoextruded balloons of the types described in U.S. Pat. No. 5,195,969,U.S. Pat. No. 5,270,086, and U.S. Pat. No. 5,478,320, or separatelyblown dual layer balloons of the types described in U.S. Pat. No.5,512,051, WO 96/04951 and in copending application Ser. No. 08/611,644,filed 6 Mar. 1996, all incorporated herein by reference, may also beemployed in the present invention by shrinking the so-formed balloon inaccordance with the present invention after it has been formed.

As further aspects of the invention, there are described herein balloonsparticularly suited to dilation of GI lesions of various types which arecharacterized by unique combinations of balloon diameter, high burststrength and high compliance characteristics.

The high strength, high compliance balloons of the invention alsoprovide excellent rewrap characteristics, in comparison to high strengthballoons formed by other processes. Consequently, after treatment of alesion and deflation of the balloon, the force required to withdraw theballoon catheter from the body is low, especially for catheters designedto pass through endoscopes (TTS).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic side view of a through-the scope dilatationcatheter of the invention.

FIG. 2 is a schematic side view of a dual lumen over-the wire dilatationcatheter of the invention.

FIG. 3 is a plot showing compliance curves of balloons prepared inExamples 3 and 4.

FIG. 4. is a plot showing compliance curves of balloons prepared inExample 5.

FIG. 5. is a plot showing compliance curves of balloons prepared inExample 6.

DETAILED DESCRIPTION OF THE INVENTION

Typically, balloon dilatation catheters for gastrointestinalapplications are available in two design options: 1) through-the scope(TTS); and 2) over-the-wire (OTW). Each design offers particularadvantages in specific clinical situations.

Referring to FIG. 1, a TTS balloon dilatation catheter 10 is shown.Catheter 10 comprises a shaft 12, a balloon 14 near the distal endthereof and an inflation apparatus 16 at the proximal end thereof. Shaft12 has a strong flexible kink-resistant construction and includes alongitudinal lumen extending therethrough by means of which the balloon14 may be inflated by the inflation apparatus 16. Catheter 10 isdesigned for direct passage through the working channel of the endoscopeto the site of an obstructive lesion. Because TTS catheters are notpassed over a guidewire, the design includes a mechanism for stiffeningthe shaft enough to allow advancement through the narrow scope channelto the lesion. To achieve this result, TTS catheters suitablyincorporate a stiffening stylet 18 within the shaft. This stylet extendsfrom the proximal end of the shaft through the length of the balloon andprovides the stiffness required to facilitate passage through anendoscope and enhance appropriate positioning within the lesion.

TTS balloon dilatation catheters are useful when an endoscopist prefersto dilate under direct visualization. With the endoscope placedimmediately proximal to the lesion, catheter advancement and ballooninflation can be directly monitored. Scope placement immediatelyproximal to the balloon also assists in maintaining proper balloonposition during inflation. For example, during dilatation of pyloricstructures, the balloon has a tendency to slip proximally or distallyduring inflation. By positioning the scope at the proximal end of theballoon, the endoscopist is able to mechanically block any backwardmovement during inflation thereby facilitating efficient, effectivedilatation.

FIG. 2 illustrates the construction of an OTW balloon dilation catheter30. Catheter 30 includes a shaft 32 which has a strong flexiblekink-resistant construction and incorporates a double-lumen design. Thisdesign provides a lumen for guidewire passage and a lumen for ballooninflation. At the proximal end of catheter 30 the lumens of shaft 32divide into separate portions 34, 36 which communicate respectively toballoon inflation apparatus 38 and to guidewire control apparatus 40. Aballoon 42 is mounted on the shaft 32 near the distal end of catheter30. Catheter 30 may incorporate a soft flexible tip 44 to provide lesstraumatic advancement through tortuous or narrow strictures. Tip 44 maybe radiopaque to assist in fluoroscopic positioning of the catheter atthe lesion site.

OTW balloon dilatation catheters are the preferred design option whenextremely tortuous of difficult anatomy is encountered. In these cases,the ability to track the catheter over a previously placed guidewireenhances the clinician's ability to precisely position the balloon foreffective dilatation. Further, for colonic lesions distal to scopeaccess, a fluoroscopically-guided, OTW placement technique can be usedto achieve appropriate positioning.

With OTW balloon dilatation catheters, the endoscopist typicallymonitors balloon inflation fluoroscopically rather than under directvisualization. Therefore, these dilators incorporate radiopaque markersto aid in accurate positioning. These catheters are designed to be usedwith guidewires and are available in a variety of shaft and balloonlengths and diameters. This allows the endoscopist to select a catheterappropriate for each lesion.

With regard to balloon size selection, for successful dilatation, theballoon must provide effective radial force against the entire length ofthe stricture. In FIGS. 1 and 2 the balloon diameter is indicated bydimension A and the dilation length indicated by dimension B. Theballoon should be long enough to dilate the entire length of thestricture. The inflated outer diameter should affect the desired degreeof dilatation.

The length of the catheter shaft required varies with the location ofthe stricture. For example, catheters 180 cm in length allow access toesophageal and pyloric lesions, while a catheter 240 cm in length isrequired for colonic strictures.

With the exception of Achalasia Balloon Dilators which are inflated withair, balloons are primarily inflated with water, saline or acontract/saline mixture. The latter is used with OTW balloon cathetersto enhance visualization. It is important not to exceed the maximuminflation pressure specified for any particular balloon catheter.Surpassing this pressure could lead to balloon rupture.

During a procedure the balloon is fully inflated to the desireddilatation diameter. Dilatation force is applied for as long asnecessary to achieve desired results. Using an inflation apparatusequipped with a pressure gauge, the balloons of the present inventionprovide a substantially wider range of stricture diameters which may betreated with a single catheter. After treatment, the deflated balloonsof the invention provide substantially reduced resistance to withdrawalof the catheter from the body compared to prior art high strengthballoons made for instance from biaxially oriented PET. In some TTSapplications measured withdrawal force through the scope for cathetersbearing balloons of the invention has been found to be only about ½ ofthe withdrawal force for corresponding catheters bearing PET balloons ofsimilar burst strength.

For esophageal balloon dilatation TTS catheters, a balloon ofapproximately 8 cm length (dimension B), having an outer diameter(dimension A) of 6 to 20 mm is suitable. The preferred length of thecatheter is 180 cm.

For pyloric balloon dilatation TTS catheters, a balloon of approximately5.5 cm length balloon, having an outer diameter of 6 to 20 mm issuitable. The preferred length of the catheter is 180 cm.

For colonic balloon dilatation TTS catheters, a balloon of approximately5.5 cm length balloon, having an outer diameter of 6 to 20 mm issuitable. The preferred length of the catheter is 240 cm.

For anastomotic balloon dilatation TTS catheters, a balloon ofapproximately 8 cm length balloon, having an outer diameter of 20-30 mmis suitable. The preferred length of the catheter is 240 cm.

Preferred balloon materials are block copolymers or blends of flexibleand rigid thermoplastic polymers. Particularily preferred arethermoplastic block copolymers characterized as follows:

the block copolymer is made up of hard segments of a polyester orpolyamide and soft segments of polyether;

-   -   the polyester hard segments are polyesters of an aromatic        dicarboxylic acid and a C₂-C₄ diol,    -   the polyamide hard segments are polyamides of C₆ or higher,        preferably C₁₀-C₁₂, carboxylic acids and C₆ or higher,        preferably C₁₀-C₁₂, organic diamines or of C₆ or higher,        preferably C₁₀-C₁₂, aliphatic ω-amino-α-acids, and    -   the polyether soft segments are polyethers of C₂-C₁₀, preferably        C₄-C₆ diols; and

the percentage by weight of the block polymer attributable to the hardsegments is between about 50% and about 98%. Suitably the blockcopolymer has a low flexural modulus, namely less than 150,000 psi,preferably less than 120,000 psi, and has a hardness, Shore D scale, ofgreater than 60. From such polymers, balloons having very highcompliance profiles can be prepared with high wall strength. The lowflexural modulus contributes to a softer feel found with the balloons ofthe invention, compared to those made of other high strength polymermaterial.

The preferred balloons of the invention are made of polyamide/polyetherblock copolymers. The polyamide/polyether block copolymers are commonlyidentified by the acronym PEBA (polyether block amide). The polyamideand polyether segments of these block copolymers may be linked throughamide linkages, however, most preferred are ester linked segmentedpolymers, i.e. polyamide/polyether polyesters. Suchpolyamide/polyether/polyester block copolymers are made by a moltenstate polycondensation reaction of a dicarboxylic polyamide and apolyether diol. The result is a short chain polyester made up of blocksof polyamide and polyether. The polyamide and polyether blocks are notmiscible. Thus the materials are characterized by a two phase structure:one is a thermoplastic region that is primarily polyamide and the otheris elastomer region that is rich in polyether. The polyamide segmentsare semicrystalline at room temperature. The generalized chemicalformula for these polyester polymers may be represented by the followingformula:

in which PA is a polyamide segment, PE is a polyether segment and therepeating number n is between 5 and 10.

The polyamide segments are suitably aliphatic polyamides, such as nylons12, 11, 9, 6, 6/12, 6/11, 6/9, or 6/6. Most preferably they are nylon 12segments. The polyamide segments may also be based on aromaticpolyamides but in such case significantly lower compliancecharacteristics are to be expected. The polyamide segments arerelatively low molecular weight, generally within the range of500-8,000, more preferably 2,000, most preferably about 3,000.

The polyether segments are aliphatic polyethers having at least 2 and nomore than 10 linear saturated aliphatic carbon atoms between etherlinkages. More preferably the ether segments have 4-6 carbons betweenether linkages, and most preferably they are poly(tetramethylene ether)segments. Examples of other polyethers which may be employed in place ofthe preferred tetramethylene ether segments include polyethylene glycol,polypropylene glycol, poly(pentamethylene ether) and poly(hexamethyleneether). The hydrocarbon portions of the polyether may be optionallybranched. An example is the polyether of 2-ethylhexane diol. Generallysuch branches will contain no more than two carbon atoms. The molecularweight of the polyether segments is suitably between about 400 and2,500, preferably between 650 and 1000.

The weight ratio of polyamide to polyether in the polyamide/polyetherpolyesters used in the invention desirably should be in the range of50/50 to 98/2, preferably between 60/30 and 92/08, more preferably,between 70/30 and 90/10.

Polyamide/polyether polyesters are sold commercially under the Pebax®trademark by Atochem North America, Inc., Philadelphia Pa. Examples ofsuitable commercially available polymers are the Pebax® 33 seriespolymers with hardness 60 and above, Shore D scale, especially Pebax®7233, 7033 and 6333. These polymers are made up of nylon 12 segments andpoly(tetramethylene ether) segments in different weight ratios andsegment lengths.

It is also possible to use other PEBA polymers with the physicalproperties specified herein and obtain similar compliance, strength andsoftness characteristics in the finished balloon.

As an alternative to polyamide elastomers, it is also possible toutilize polyester/polyether segmented block copolymers and obtainsimilar balloon properties. Such polymers are made up of at least twopolyester and at least two polyether segments. The polyether segmentsare the same as previously described for the polyamide/polyether blockcopolymers useful in the invention. The polyester segments arepolyesters of an aromatic dicarboxylic acid and a two to four carbondiol.

Suitable dicarboxylic acids used to prepare the polyester segments ofthe polyester/polyether block copolymers are ortho-, meta- orpara-phthalic acid, napthalenedicarboxylic acid ormeta-terphenyl-4,4′-dicarboxylic acids.

Preferred polyester/polyether block copolymers are poly(butyleneterephthalate)-block-poly(tetramethylene oxide) polymers such as ArnitelEM 740, sold by DSM Engineering Plastics. Hytrel polymers, sold byDuPont which meet the physical and chemical specifications set outherein can also be used.

It is preferred that the block copolymers have a hardness, Shore Dscale, of at least 60 and a flexural modulus of no more than about150,000, in order to obtain optimal strength, compliance and softnesscharacteristics. Preferably the Shore D hardness is in the range of65-75 and the flexural modulus is in the range of 50,000. The preferredpolymers useful in the invention are also characterized by a highultimate elongation of about 300% or higher and an ultimate tensilestrength of at least 6,000 psi.

Other thermoplastic polymer materials which may be used to prepareballoons in accordance with the invention include blends of rigid andflexible polymers; polyurethanes which have flexible portions, typicallyderived from polyester or polyether polyols and rigid portions,typically derived from diisocyanates; random copolymers of rigid andflexible monomers; aliphatic polyketones; polysulfides such as PPS(polyphenylenesulfide); polyamides, for instance C₆ or higher polyamideswhich are saturated with water, C₁₁ or higher polyamide homopolymersregardless of water content, and polyamide copolymers of linear andbranched monomer units; and other polymers or polymer blends which areknown in the art as thermoplastic elastomers. Specific additionalthermoplastic polymer products which are considered suitable includepolyurethane/polycarbonate blend or block copolymers sold under thetrademarks, TEXIN TPU by Bayer Corp and TECOTHANE by Thermedics Inc. andpolyurethanes sold under the trademark PELLETHANE by Dow Chemical Co. Aspreviously mentioned, multilayer balloon structures formed by concentriccoextrusion of different thermoplastic polymers, or by sequentialconcentric blowing of separate tubing parisons of different materials,may also be employed.

Manufacture of balloons of the invention is started with an extrudedtubing of the thermoplastic polymer material.

The balloon, prior to its being shrunk, may be manufactured inaccordance with known techniques such as described in copendingapplication Ser. No. 08/397,837, filed 2 Mar. 1995, entitled BlockCopolymer Elastomer Catheter Balloons, incorporated herein by reference,which corresponds to WO 95/23619, and Ser. No. 08/555,219, filed 8 Nov.1995, entitled Method of Balloon Formation by Cold Drawing/Necking,incorporated herein by reference. Multi-staged blowing techniques asdescribed in copending application Ser. No. 08/197,639, filed 17 Feb.1994, also incorporated herein by reference, may also be employed.

The balloon shrinking process is similar to that described in U.S. Pat.No. 5,348,538 for balloons of non-compliant material such as PET.However, the balloons of the invention are desirably constructed byblowing the balloon from a block copolymer or other polymer material asdescribed above and then shrinking the balloon to a greater extent thanwas done in the specific illustrative examples of U.S. Pat. No.5,348,538. The amount of shrinkage is controlled by the pressuremaintained in the balloon during annealing and the temperature and timeof the annealing. For a balloon made from Pebax® 7233, the blowingpressure is suitably in the range 200-400 psi, and temperature issuitably in the range of 90-100° C., and the annealing pressure is inthe range of 0-50, preferably 1-30 psi at 70-100° C. for 3-30 seconds.

By shrinking until the balloon, at 3 atm pressure, provides a diameterof about 90% or less, preferably 85% or less, and more preferably about65%-75% of the diameter of a correspondingly prepared balloon, at 3 atmpressure, which does not undergo shrinking, a very steep compliancecurve is obtained which is more generally linear, the greater theshrinkage. Burst strength is not substantially affected by the shrinkingstep. However the shrinking step causes the compliance curve to startfrom a lower point so that overall the balloon is much more compliant.In this manner the comparatively high strength of the block copolymermaterial is made accessible to medical device applications where highcompliance is also desirable.

To improve balloon-to-balloon reproducibility of the process, theballoon may be shrunk at a very low inflation pressure (typically 0-30psi) to a nominal diameter below that desired in the final balloon, andthen pressurized at a pressure between the shrink pressure and 50 psi,at a temperature within the same range within a mold or cylinder whichis sized to provide the desired nominal diameter, still below thediameter at which the balloon was initially blown, and suitably 90% orless of the initial blow diameter. Example 10 is illustrative of thistechnique.

The invention is illustrated by the following non-limiting examples.

EXAMPLE 1(COMPARATIVE EXAMPLE)

Pebax® 7233 tubes with dimensions of 0.105 inch ID (innerdiameter)×0.140 OD (outer diameter) are cold-drawn at a very lowtemperature, approximately in the range of −100° C. to −20° C. asfollows. A screw driven stretching machine with a pair of pneumaticgrippers is used to stretch the tubing. The center portion of the tubeis cooled by directly spraying liquid N₂ on the center portion. Five 50mm length balloons are blown at 95° C. in a 16 mm diameter mold using ablowing pressure of 260 psi and a tension of 160 grams. The averagedouble wall thickness of the balloons was 0.00282 inch. The burstpressure was 9.2 atm. The compliance from 3 atm to 5 atm was 4.2% andfrom 3 atm to burst pressure was 11.7%.

EXAMPLE 2

Five balloons were prepared as in Example 1. The balloons, whileinflated at about 5 psi pressure, were shrunk by dipping in a 80° C.water bath for 5 minutes. The average double wall thickness aftershrinking was 0.00429 inch. The average burst pressure of the balloonswas 9.4 atm. The compliance from 3 atm to 5 atm was 15% and from 3 atmto burst pressure was 39%.

EXAMPLE 3 (COMPARATIVE EXAMPLE)

Pebax® 7233 tubes with dimensions of 0.0264 inch ID×0.0464 OD (outerdiameter) are cold-drawn as in Example 1. A 4 mm balloon is blown at 95°C. in a mold using a blowing pressure of 450 psi and a tension of 300grams. The burst pressure was 22 atm.

EXAMPLE 4

The process of Example 2 is repeated except that the shrinking step isperformed by annealing the balloons while inflated to 2 atm pressure inwater baths under different conditions, namely: 75° C. for 10 seconds;75° C. for 30 seconds; 75° C. for 60 seconds; and 95° C. for 10 seconds.Compliance curves for the balloons of Examples 3 and 4 are plotted inFIG. 3.

EXAMPLE 5

Balloons were prepared as in Examples 1 and 2 using Pebax 7033 polymerand the conditions specified in Table 1. The compliance results aresummarized in Table 1 and are plotted in FIG. 4.

EXAMPLE 6

Balloons were made from Amitel EM 740 polymer tubing by stretchingtubing as specified in Table 2 at room temperature at a stretch ratio of4.2 and then blowing the balloon from the stretched tubing under theconditions specified in Table 2. The compliance results are summarizedin Table 2 and are plotted in FIG. 5. TABLE 1 Mold Blowing Double DiaLength Tube ID × OD pressure Blowing wall Shrinking Shrinking Burstpressure Compliance 3 Compliance Sample (mm) (mm) (inch) (atm) tension(g) thickness temp. ° C. time\min (atm) atm-burst % %/atm 5A 9 50 .0515× .0545 400 130 .00213 none none 15 15% 1.25 5B 9 50 .0515 × .0545 400130 .00285 80 5 14 49% 4.45 5C 12 50  .098 × 0.132 300 190 .00281 nonenone 11 15% 1.375 5D 12 50  .098 × 0.132 300 190 .0044 81 5 11 47% 5.8755E 18 50 0.118 × 0.158 350 250 .00295 none none 10 11% 1.83 5F 18 500.118 × 0.158 350 250 .00457 81 5 9 28% 4.66 5G 20 80 0.135 × 0.175 300175 .00290 none none 9  9% 1.50 5H 20 80 0.135 × 0.175 300 175 .00413 801 9 27% 4.50

TABLE 2 Mold Tube Blowing Burst Diameter Length ID × OD pressure BlowingDouble wall Shrinking Shrinking pressure Compliance 3 Compliance (mm)(mm) (inch) (atm) tension (g) thickness temp. ° C. time\min (atm)atm-burst % %/atm 5.5 50 .046 × .084 350 none .00275 none none 16 27%2.00 5.5 50 .046 × .084 350 none .00360 80 1 16 70% 5.38

As can be seen from FIGS. 3-5, the balloons prepared utilizing theshrinking step have very high compliance profiles, in addition to highwall strength. The shrinking step causes the compliance curve to startfrom a lower point so that overall the balloon is much more compliant.In this manner the comparatively high strength of the block copolymermaterial is made accessible to medical device applications where highcompliance is also desirable.

EXAMPLE 9 (COMPARATIVE EXAMPLE)

Extruded Pebax 7233 tubes with dimensions of 0.0509 inch ID×0.0729 inchOD were prepared. Five 55 mm length balloons were blown at a temperatureof 95° C. in an 8 mm diameter mold using a blowing pressure of 450 psiand a tension of 150 grams. The average double wall thickness of theballoons was 0.00174 inch. The average burst pressure was 13.6 atm. Thecompliance from 3 atm to 10 atm was 9.0%, and from 3 atm to burstpressure was 15%.

EXAMPLE 10

Five balloons were prepared as in Example 9. The balloons while at atension and inflated at atmospheric pressure were shrunk by dipping inan 85° C. water bath for 2 minutes. The balloons were then each insertedinto a 5.6 mm ID glass tube, replaced in the 85° bath and pressurized at30 psi for 2 minutes. The resulting balloons had an average double wallthickness of 0.00233 inch, an average burst pressure of 12.6 mm, acompliance from 3 atm to 10 atm of 36% and a compliance from 3 atm toburst of 44%.

The above disclosure is intended to be illustrative and not exhaustive.These examples and description will suggest many variations andalternatives to one of ordinary skill in this art. All thesealternatives and variations are intended to be included within the scopeof the attached claims. Those familiar with the art may recognize otherequivalents to the specific embodiments described herein whichequivalents are also intended to be encompassed by the claims attachedhereto.

1-34. (canceled)
 35. A balloon for a medical device made by a methodwherein a tubing of a thermoplastic polymer material is radiallyexpanded under a first elevated pressure at an elevated temperature toform the balloon at a first diameter, the thermoplastic polymer materialbeing a block copolymer material and the method including the furtherstep of annealing the balloon at a second elevated temperature less thanthe first elevated temperature and a second pressure less than the firstelevated pressure for a time sufficient to shrink the formed balloon toa second diameter less than the first diameter, and wherein saidannealing step occurs prior to sterilization of the medical device. 36.A balloon as in claim 35 having an operating pressure to which theballoon may be safely inflated without bursting of at least 12atmospheres, a diameter at 3 atmospheres of from about 1.5 to about 6.0mm and a diameter growth of at least 1.0 mm over the range of 3-12 atm.37. A balloon as in claim 35 having an operating pressure to which theballoon may be safely inflated without bursting of at least 10atmospheres, a diameter at 3 atmospheres of from about 6 to about 12 mmand a diameter growth of at least 2 mm over the range of 3-10 atm.
 38. Aballoon as in claim 35 having an operating pressure to which the balloonmay be safely inflated without bursting of at least 9 atmospheres, adiameter at 3 atmospheres of from about 12 to about 30 mm and a diametergrowth of at least 3 mm over the range of 3-9 atm.
 39. A balloon as inclaim 38 wherein said diameter growth is at least 4 mm.
 40. A balloon asin claim 35 that has been sterilized subsequent to said annealing step.41. A balloon for a medical device having a diameter at 3 atmospheresinflation pressure of at least 5 mm, a burst pressure of at least 9atmospheres, and a growth rate in the range of 3 atmospheres to burst ofat least 4% per atmosphere.
 42. A balloon as in claim 41 wherein saiddiameter at 3 atmospheres is from about 6 to about 12 mm, the balloonfurther characterized by an operating pressure to which the balloon maybe safely inflated without bursting of at least 10 atmospheres and adiameter growth of at least 2 mm over the range of 3-10 atmospheres. 43.A balloon as in claim 41 wherein said diameter at 3 atmospheres is atleast 12 mm and said balloon has a diameter growth of at least 3 mm overthe range of 3-9 atmospheres.
 44. A balloon as in claim 43 wherein saiddiameter growth over the range of 3-9 atmospheres is at least 4 mm. 45.A balloon as in claim 43 wherein said diameter at 3 atmospheres is inthe range of about 12 to about 18 mm.
 46. A balloon is in claim 41 madefrom thermoplastic polymer material selected from the group consistingof block copolymers, thermoplastic elastomers, polymer blends, randomcopolymers of rigid and flexible monomers, polyurethanes which haverigid and flexible portions, polyketones, polysulfides and polyamidehomopolymers and copolymers.
 47. A balloon as in claim 41 formed from atleast two concentric layers of different thermoplastic polymers.
 48. Aballoon as in claim 41 having a double wall thickness of about 0.00457inches or less.
 49. A balloon as in claim 41 wherein said diameter at 3atmospheres is about in the range of 6-30 mm.
 50. A balloon as in claim41 wherein said diameter at 3 atmospheres is about 12 mm or more.
 51. Acatheter for treatment of a gastrointestional lesion comprising aballoon as in claim
 41. 52. A medical device balloon formed by a methodcomprising: radially expanding tubing of thermoplastic polymer materialunder elevated blowing pressure greater than 50 psi at an elevatedblowing temperature to form the balloon to have a first diameter at 3atm inflation pressure, annealing the formed balloon prior tosterilization of the medical device at an elevated annealing temperatureless than or equal to the blowing temperature, and at an annealingpressure which in the range of 0-20 psi, for a time sufficient to shrinkthe formed balloon to have a second diameter at 3 atm inflation pressurewhich is less than 90% of the first diameter, and then pressurizing theballoon in a fixed diameter form, said fixed diameter being greater thansaid second diameter but no more than 90% of said first diameter, at apressure above the annealing pressure but no more than 50 psi and atemperature not less than said annealing temperature and not greaterthan said blowing temperature for a time to provide the balloon with afinal diameter at 3 atm inflation pressure which is greater than saidsecond diameter but not more than 90% of said first diameter.
 53. Amedical device balloon as in claim 51 wherein said final diameter is 85%or less of said first diameter.
 54. A medical device balloon as in claim51 wherein said final diameter is 65-75% of said first diameter.
 55. Amedical device balloon as in claim 51 wherein the thermoplastic polymermaterial is a block copolymer, a thermoplastic elastomer, a polymerblend, a random copolymer of rigid and flexible monomers, polyurethaneswhich have rigid and flexible portions, polyketones, polysulfides or apolyamide homopolymer or copolymer.